[go: up one dir, main page]

WO2005023921A1 - Procede de production en continu d'un film fonctionnel - Google Patents

Procede de production en continu d'un film fonctionnel Download PDF

Info

Publication number
WO2005023921A1
WO2005023921A1 PCT/JP2004/006389 JP2004006389W WO2005023921A1 WO 2005023921 A1 WO2005023921 A1 WO 2005023921A1 JP 2004006389 W JP2004006389 W JP 2004006389W WO 2005023921 A1 WO2005023921 A1 WO 2005023921A1
Authority
WO
WIPO (PCT)
Prior art keywords
sheet
resin film
polymer
film
precursor
Prior art date
Application number
PCT/JP2004/006389
Other languages
English (en)
Japanese (ja)
Inventor
Hideki Hiraoka
Kouzou Kubota
Takeo Yamaguchi
Nobuo Ooya
Hiroshi Harada
Original Assignee
Toagosei Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to CA002537795A priority Critical patent/CA2537795A1/fr
Priority to US10/570,609 priority patent/US7674349B2/en
Publication of WO2005023921A1 publication Critical patent/WO2005023921A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0093—Chemical modification
    • B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5618—Impregnating foam articles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H01M8/106—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties characterised by the chemical composition of the porous support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. in situ polymerisation or in situ crosslinking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/30—Cross-linking
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10T156/11—Methods of delaminating, per se; i.e., separating at bonding face
    • Y10T156/1168—Gripping and pulling work apart during delaminating

Definitions

  • the present invention relates to a method for continuously producing a functional film. More specifically, the present invention relates to a method for continuously producing a functional film in which a functional film in which pores of a porous resin sheet are filled with a functional polymer can be efficiently and continuously obtained.
  • the present invention can be used in batteries such as fuel cells and redox flow batteries, various devices in electrolysis and the like, and separation membranes.
  • Functional membranes obtained by filling a porous membrane with various functional polymers such as a polymer obtained by polymerizing a monomer having an ion exchange group are used in many applications.
  • a fuel cell which is one type of an electrochemical device using an electrolyte membrane in which a polymer electrolyte body is filled in a porous membrane.
  • the performance of this fuel cell has been greatly improved due to improvements in electrolyte membrane and catalyst technology, and is being developed for use in low-emission vehicles.
  • Such a functional film is produced by impregnating a porous film with a functional monomer and the like, and then polymerizing the functional monomer and the like.
  • a method is known in which both sides of the porous film are covered with a polyester film as a release material during the polymerization, and then heated under nitrogen pressure (for example, see Patent Document 1).
  • Patent Document 1 JP-A-11-335473
  • Patent Document 1 describes that a porous film is sandwiched between films as a release material during polymerization. However, this document does not disclose a method for continuously and efficiently producing a functional film in which a polymer is filled in pores of a porous resin sheet.
  • the present invention has been made in view of the above-mentioned circumstances, and is intended to prevent a polymer precursor impregnated and continuously attached to a continuously conveyed porous resin sheet from dropping off, and particularly to reduce the vicinity of the surface.
  • Functional membranes that have no defects such as unfilled polymer It is an object of the present invention to provide a method for continuously producing a functional film that can be obtained continuously and efficiently.
  • the present invention is as follows.
  • a porous resin sheet is continuously conveyed, and the porous resin sheet is impregnated with a polymer precursor containing a monomer having a functional functional group, and is impregnated and adhered. Precursor impregnation with polymer precursor impregnated and attached
  • the first resin film is continuously supplied to one side of the adhered sheet and brought into contact with the precursor, and the precursor is impregnated.
  • the second resin film is continuously supplied and brought into contact with the other side of the adhered sheet to be impregnated with the precursor.
  • a method for continuously producing a functional film comprising:
  • At least one of the first resin film and the second resin film forms a closed loop in the longitudinal direction, and contacts the precursor-impregnated / adhered sheet while rotating as described in 1. or 2. 5.
  • At least one of the first resin film and the second resin film is a resin film through which active energy rays can pass, and the polymerization is carried out from the side of the resin film through which active energy rays can pass. 4.
  • the first resin film and the second resin film have different thicknesses, and the thin resin finolem can transmit active energy rays, and the active energy rays are irradiated from the thin resin film side. 4.
  • a resin film is continuously supplied to one side and the other side of a porous resin sheet, and the polymer is sandwiched between the resin films.
  • a functional polymer is filled in the pores of the porous resin sheet, and a functional film free from defects such as not filled with polymer in the vicinity of the surface can be continuously and efficiently obtained. be able to.
  • an electrolyte membrane which is one type of a functional membrane, can be efficiently produced.
  • the polymer is filled.
  • At least one of the first resin film and the second resin film is a resin film through which the active energy ray can pass, and the polymerization is performed by irradiating the active energy ray from the side of the resin film through which the active energy ray can pass.
  • the polymerization is performed by irradiating the active energy ray from the side of the resin film through which the active energy ray can pass.
  • the first resin film and the second resin film have different thicknesses, and the thin resin film can transmit active energy rays, and the active energy rays are thin. Polymerization can be carried out efficiently at the dose, and the precursor impregnated and adhered sheet can be sufficiently supported by the thick resin film.
  • the precursor-impregnated 'adhered sheet can be transported smoothly.
  • a functional film can be manufactured more efficiently.
  • Impregnation and adhesion process The above “porous resin sheet” is continuously conveyed.
  • the porous resin sheet usually, a long sheet wound around a core is used, and the long sheet is continuously conveyed at a predetermined speed.
  • the transport speed is not particularly limited, the force S can be set to 0.01 to 100 m / min, and it is preferable to set the transport speed to 1 to 50 mZ.
  • the resin used to form the porous resin sheet is not particularly limited.
  • Polyolefin resins such as polyethylene and polypropylene, polychlorinated vinyl, vinyl chloride monobutyl acetate copolymer, and vinyl chloride monochloride vinylidene copolymer ,
  • Vinyl chloride resins such as chlorofluoroethylene copolymer, polytetrafluoroethylene, polytrifluoroethylene, polychlorotrifluoroethylene, poly (tetrafluoroethylene-hexafluoroethylene) Fluorine resins such as propylene) and poly (tetrafluoroethylene-perfluoroalkyl ether), polyamide resins such as nylon 6 and nylon 66, aromatic polyimides, aramides, polysulfones and polyether ether ketones.
  • a polyolefin resin excellent in mechanical strength, chemical stability, chemical resistance and the like is preferable.
  • a porous resin sheet which is cross-linked by electron beam irradiation, chemical cross-linking with a cross-linking agent, etc. and has improved heat resistance and the like is preferable.
  • a porous resin sheet which increases strength by stretching or the like and suppresses deformation due to external force is preferable.
  • a porous resin sheet obtained by combining crosslinking and stretching is more preferable.
  • the porosity of the porous resin sheet is preferably 5 to 95%, particularly 5 to 90%, more preferably 20 to 80%, depending on the type of the polymer, the use of the porous resin sheet, and the product to be used. .
  • the average pore diameter is in a preferred range depending on the type of polymer, the product in which the porous resin sheet is used, etc.
  • Force S Different force 0.001 to 100 ⁇ , particularly 0.01 to lzm.
  • the porosity of the porous resin sheet is 595%, especially 5 to 90. /. And 20-80. /.
  • the average diameter of the mosquitoes is preferably 0.001 100 ⁇ , especially 0.011 xm.
  • the thickness of the porous resin sheet also depends on the type of the polymer, the use of the porous resin sheet, the product to be used, and the like, but is preferably 200 zm or less. It is preferable that the force S be 1 to 150 m, especially 5 to 100 ⁇ m, and more preferably 5 to 50 ⁇ m. If the porous resin sheet is too thin, the strength is reduced.
  • the porous resin sheet when used as an electrolyte membrane for a fuel cell, the crossover amount of hydrogen and methanol increases, which is not preferable.
  • the thickness is too large, the membrane resistance becomes excessive and the output decreases, which is not preferable.
  • the thickness variation of the porous resin sheet is preferably ⁇ 5% or less, more preferably ⁇ 1% or less.
  • the tensile elastic modulus of the porous resin sheet is preferably 500 to 5000 MPa, particularly preferably 1000 to 5000 MPa.
  • the tensile strength at break of the porous resin sheet is preferably 50 500 MPa, particularly preferably 100 500 MPa.
  • the tensile elastic modulus of the porous resin sheet is preferably 500 to 5000 MPa, particularly 1000 to 5000 MPa, and the tensile strength at break is preferably 500 to 500 MPa, particularly 100 to 500 MPa. If the porous resin sheet has a tensile modulus of at least one of 500-5000 MPa and a tensile breaking strength of at least one of 50-500 MPa, the porous resin sheet has appropriate rigidity.
  • a functional membrane may be used as an electrolyte membrane for a fuel cell. Cracks do not occur due to pressure molding during electrode bonding and tightening during battery assembly when using.
  • the fuel cell is preferably a porous resin sheet that has sufficient heat resistance at this temperature to raise the temperature during operation and does not easily deform even when an external force is applied.
  • the "polymer precursor” contains a monomer having a functional functional group.
  • a monomer having a functional functional group As the above “monomer having a functional functional group” (hereinafter, referred to as “functional monomer”), various monomers can be used depending on the purpose and use of the functional film.
  • the functional monomer include a monomer having an ion exchange group used when the functional membrane is an electrolyte membrane in fuel cells and electrolysis, and a functional membrane used as a separation membrane in concentration and the like. Examples thereof include a monomer having a polar group or a non-polar group to be used.
  • the monomer having an ion-exchange group used when the functional membrane is an electrolyte membrane in a fuel cell or the like is preferably a monomer having a proton acid group which is excellent in performance when used as an electrolyte membrane for a fuel cell. .
  • the monomer having a protonic acid group is a compound having a polymerizable functional group and a protonic acid in one molecule, for example, 2_ (meth) atalinole Amido-2-methylpropanesulfonic acid, styrenesulfonic acid, (meth) arylsulfonic acid, vinylsulfonic acid, isoprenesulfonic acid, (meth) acrylic acid, maleic acid, crotonic acid, burphosphonic acid, containing an acidic phosphoric acid group (meth) Atarilate and the like. Only one of these functional monomers may be used, or two or more of them may be used.
  • “(meth) aryl” and “(meth) atalylate” mean “atalylate and / or metathalilate” (the same applies to the following).
  • a monomer having a functional group that can be converted into an ion exchange group can also be used.
  • the monomer include salts, anhydrides and esters of the above compounds.
  • the acid residue of the monomer used is a derivative such as a salt, an anhydride or an ester
  • proton conductivity can be imparted by converting the monomer into a proton acid type after polymerization.
  • a monomer having a site into which an ion exchange group can be introduced after polymerization may be used. Examples of this monomer include monomers having a benzene ring, such as styrene, ⁇ -methylstyrene, chloromethylstyrene, and t-butylstyrene.
  • Examples of a method for introducing an ion exchange group into these monomers include a method of sulfonating with a sulfonating agent such as chlorosulfonic acid, concentrated sulfuric acid, and sulfur trioxide.
  • a sulfonating agent such as chlorosulfonic acid, concentrated sulfuric acid, and sulfur trioxide.
  • One of these monomers may be used alone, or two or more thereof may be used.
  • a vinyl compound having a sulfonic acid group and a vinyl compound having a phosphoric acid group having excellent proton conductivity are preferred, and 2- (meth) acrylamide-2-methylpropane sulfone having high polymerizability is preferred. Les, especially preferred with acid.
  • Examples of the monomer having an ion exchange group used when the functional membrane is an electrolyte membrane for electrolysis and the like include 2- (meth) acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth) Examples include monomers having a proton acidic group such as acrylsulfonic acid, butylsulfonic acid, maleic acid and crotonic acid, and basic monomers such as butylpyridine and p_butyl_N, N-dimethylbenzylamine. One of these monomers may be used alone, or two or more thereof may be used.
  • Examples of the monomer having a polar group or a non-polar group used when the functional membrane is a separation membrane for concentration or the like include unsaturated organic acids such as (meth) acrylic acid, maleic acid, crotonic acid, and esters thereof. , Amide, Derivatives such as imides and salts, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, cyclo (meth) acrylate (Meth) acrylates such as hexyl, lauryl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) atalinoleate, styrene, polymethylstyrene, N-vinylolepyrrolidone, and butylpyridine No.
  • One of these monomers may be used alone, or two or more thereof
  • the polymer precursor contains a functional monomer, which may be composed of only a functional monomer, and another monomer copolymerizable with the functional monomer (hereinafter, referred to as "other monomer"). May be. Further, the polymer precursor may contain a functional monomer which may or may not contain a functional monomer and a crosslinkable monomer, another monomer, and a crosslinkable monomer.
  • the functional monomer is a monomer having an ion exchange group used for forming an electrolyte membrane in a fuel cell or the like
  • a monomer having no proton acidic group can be contained as the other monomer.
  • the other monomer is not particularly limited as long as it is a monomer having an ion-exchange group, a monomer copolymerizable with a crosslinkable monomer, and the like.
  • Examples of the monomer include (meth) acrylates, (meth) acrylamides, maleimides, Examples include styrenes, organic acid burs, aryl compounds and methallyl compounds. One of these monomers may be used alone, or two or more thereof may be used.
  • the functional monomer when the functional monomer is a monomer having an ion-exchange group used for forming an electrolyte membrane in electrolysis or the like, an ion-exchange group may be used as another monomer to improve strength, adjust hydrophilicity, or the like.
  • Monomers that do not have, crosslinkable monomers and the like can be contained. One of these monomers may be used alone, or two or more thereof may be used.
  • a cross-linking monomer or the like When the functional monomer is a monomer having a polar group or a non-polar group used for forming a separation membrane during concentration or the like, a cross-linking monomer or the like may be added as another monomer to improve strength or the like. Can be. One of these monomers may be used alone, or two or more thereof may be used.
  • crosslinkable monomer a monomer having two or more polymerizable functional groups in one molecule. Nomers can be used.
  • the crosslinkable monomer include N, ⁇ ′-methylenebis (meth) acrylamide, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol propane diaryl ether, and pentaerythritol. Retarialine ethereol, dibutylbenzene, bisphenol di (meth) atalylate, isocyanuric acid di (meth) atalylate, tetraaryloxetane, triarinoleamine, diaryloxyacetate and the like.
  • the crosslinkable monomer is not limited to one having a carbon-carbon double bond, and a bifunctional or more functional epoxy conjugate may be used although the reaction rate is slightly lower.
  • a crosslink bond is formed by reacting with a carboxinole group or the like of the polymer.
  • the crosslinkable monomer only one kind may be used, or two or more kinds may be used.
  • porous resin sheet can be impregnated and adhered with various components other than the polymer precursor such as a polymerization initiator, an antioxidant, an ultraviolet absorber, and a colorant, if necessary.
  • Impregnation and adhesion of the polymer precursor and the like are carried out by impregnating the polymer precursor and the like into the pores of a long porous resin sheet that is continuously conveyed, and attaching the polymer precursor to the surface of the porous resin sheet. And the like can be attached.
  • the method of impregnation and adhesion is not particularly limited, and a method of immersing the porous resin sheet in a polymer precursor or the like, or a solution or dispersion in which the polymer precursor or the like is dissolved or dispersed in a solvent, and Or a method of spraying a solution or dispersion obtained by dissolving or dispersing a polymer precursor or the like in a solvent onto a porous resin sheet.
  • a method for impregnation and adhesion a method in which the porous resin sheet is immersed in a solution or dispersion obtained by dissolving or dispersing a polymer precursor or the like in a solvent is preferable.
  • the polymer precursor and the like can be uniformly impregnated and adhered to the porous resin sheet.
  • the porosity and average pore diameter of the porous resin sheet and the polymer precursor and the like are preferably used.
  • the temperature, time, and the like during the impregnation and adhesion are not particularly limited, but the temperature is preferably 0 to 120 ° C, particularly 580 ° C, and more preferably 5 to 50 ° C.
  • Time is 0.1 second to 1 hour, especially 1 second Preferably, it is set to one ten minutes, more preferably one second to five minutes.
  • the temperature should be 0-120 ° C, especially 5-80 ° C, and 5-50 ° C, and the time should be 0.1 second-1 hour, especially 1 second-10 minutes, and 1 second-15 minutes. Is more preferable.
  • Each component such as the polymer precursor itself can be impregnated and adhered as it is if it is a liquid itself, especially a liquid having a viscosity low enough to be impregnable.
  • the preferred viscosity in this case is 11OOOOmPa's.
  • a solution or dispersion obtained by dissolving or dispersing each component such as a polymer precursor in a solvent can be impregnated and adhered.
  • the viscosity of this solution or dispersion is also preferably 11 OOOOmPa ⁇ s.
  • various components such as a polymerization initiator
  • they can be impregnated and adhered separately from the polymer precursor.
  • at least one of various components such as a polymerization initiator and a polymer precursor can be mixed and impregnated and adhered simultaneously.
  • all of various components such as a polymerization initiator can be mixed with a polymer precursor and simultaneously impregnated and adhered.
  • the respective components By simultaneously impregnating and adhering at least one of the various components such as the polymerization initiator, preferably all the components such as the polymerization initiator, and the polymer precursor, the respective components become porous resin. It can be more uniformly impregnated in the pores of the sheet.
  • Polymerization of the polymer precursor can be performed by irradiation with active energy rays such as ultraviolet rays, electron beams, and visible rays and thermal polymerization by heating.
  • active energy rays such as ultraviolet rays, electron beams, and visible rays and thermal polymerization by heating.
  • the “first resin film” is continuously supplied to one surface of the “precursor-impregnated 'adhered sheet'” impregnated and adhered with the polymer precursor and the like, and is contacted with the other surface.
  • Continuous supply of “resin film” The contact is carried out in a state where the precursor-impregnated adhesion sheet is sandwiched between the first resin film and the second resin film.
  • the state of this contact is not particularly limited as long as the porous resin sheet or the like can be smoothly conveyed at a predetermined speed, and the impregnated polymer precursor or the like does not fall off before polymerization. If the polymer precursor and the like are prevented from falling off in this way, the polymer is sufficiently filled in the pores up to the inside of the surface force, and a functional film without defects can be obtained. Further, it is preferable that the first and second resin films and the precursor-impregnated 'attachment sheet' are in close contact with each other so that gas such as air does not enter each interface. If the invasion of air or the like is prevented in this way, the polymerization is not hindered, particularly when a radical polymerizable polymer precursor is used, and a functional film can be produced more efficiently.
  • the first resin film 21 and the second resin film 22 can be continuously fed from the film supply sources 211 and 221, respectively, supplied and brought into contact with the precursor-impregnated / adhered sheet (see FIG. 2). ).
  • the film supply source a long film wound on a core is usually used, and the first and second resin films delivered from the film supply source and supplied are respectively impregnated with the precursor.
  • the “precursor-impregnated” adhering sheet that comes into contact with one surface of the adhering sheet 11 and the other surface is conveyed while being sandwiched between two resin films.
  • the polymer precursor can be polymerized by irradiating an active energy ray such as an ultraviolet ray or an electron beam from at least one resin finolem side. Further, each of the transported resin films and the precursor-impregnated / adhered sheet can be heated to thermally polymerize the polymer precursor. Also in Figure 2
  • the precursor-impregnated / adhered sheet is conveyed in the horizontal direction, but may be conveyed in a vertical direction or may be inclined. Further, it may be conveyed from below to above, or may be conveyed from above to below.
  • the first and second resin films can be separated from the precursor-impregnated / adhered sheet, wound around a core, and stored. Each resin film wound around this core can be reused until it becomes unusable due to fouling, wrinkles, elongation and the like.
  • the first resin film 21 is continuously fed from the film supply source 211, supplied and brought into contact with the precursor impregnated 'attachment sheet 11, and the second resin film 22 is closed in the longitudinal direction.
  • the film is formed into a loop, and the film can be brought into continuous contact with the precursor impregnated 'adhering sheet while rotating (see Fig. 3).
  • the first resin film sent from the film supply source and supplied is conveyed together with the precursor-impregnated 'adhesion sheet while being in contact with one surface of the precursor-impregnated' adhesion sheet.
  • the rotating second resin film is in continuous contact with the other surface of the precursor-impregnated / adhered sheet, and the precursor-impregnated / adhered sheet is conveyed sandwiched between the two resin films.
  • the polymer precursor can be polymerized by irradiating it with an active energy ray, or polymerized by heating.
  • the precursor-impregnated 'adhered sheet and the like are conveyed in the horizontal direction, but the conveyance direction may be inclined or may be conveyed in the vertical direction. Further, the lower force may be conveyed upward, or may be conveyed downward from above.
  • the first resin film can be peeled off from the precursor-impregnated / adhered sheet, wound around a core and stored.
  • the resin film wound around the core can be reused until it becomes unusable due to fouling, wrinkles, elongation and the like.
  • the second resin film can be continuously used until it becomes unusable due to staining, wrinkles, elongation, and the like.
  • first resin film 21 and the second resin film 22 are each a film forming a closed loop in the longitudinal direction, and these films facing each other at a predetermined interval are rotated, and the gap between the films is formed.
  • the precursor-impregnated / adhered sheet 11 to be conveyed may be brought into continuous contact with the first and second resin films, and the precursor-impregnated / adhered sheet may be conveyed while being sandwiched between two resin films. Yes (see Figure 4).
  • the polymer precursor can be polymerized by irradiating it with active energy rays, or polymerized by heating.
  • the precursor impregnated / adhered sheet and the like are conveyed in the horizontal direction, but the conveyance direction may be inclined or may be conveyed in the vertical direction. Further, it may be conveyed from below to above or from above to below.
  • the first resin film and the second resin film can be repeatedly used until they become unusable due to fouling, wrinkles, elongation and the like.
  • the first resin film and the second resin film are used to impregnate the precursor-impregnated sheet sandwiched between these films, and to prevent the polymer precursor adhering to the polymer sheet from adhering to the polymer sheet to smoothly progress the polymerization. It is desirable that the transmittance be low.
  • ASTM D 1434-72 of these films Oxygen permeability at 25 ° C measured according to the, 5000 ml / m ⁇ 24 hours' MPa or less, especially 3000 ml / m 2 'and the 24-hour' MPa or less, further 1500 ml / m 2 'Dearuko 24 hours' MPa preferable.
  • the resin forming each of the first resin film and the second resin film is not particularly limited. Further, the first resin film and the second resin film may be made of the same kind of resin, or may be made of different resin strengths.
  • the resin may be a thermoplastic resin or a thermosetting resin, but a thermoplastic resin that can easily form a film having high strength is preferred.
  • the thermoplastic resin include polyesters (eg, 770) such as polyethylene terephthalate and polybutylene terephthalate, polyolefins such as polyethylene (eg, 81000), polypropylene (eg, 16200), and polyamides (eg, nylon 6 and nylon 66).
  • polyvinyl chloride for example, 1400
  • polyvinylidene chloride for example, 300
  • regenerated cellulose for example, 60
  • polycarbonate for example, 36500
  • polyphenylene sulfide for example, 2070.
  • the value in parentheses is the oxygen permeability of each resin measured at 25 ° C measured by the above method. However, the thickness of the film used for measurement is 25 ⁇ , and the unit is ml / m 2 '24 hours' is MPa.
  • these thermoplastic resins there are compounds which are hardly deteriorated and hardly deformed due to irradiation of active compounds such as ultraviolet rays and electron beams, heating during thermal polymerization, etc.
  • Polyolefin and polyvinylidene chloride are preferred. Further, a film made of polyester and polyolefin is also preferable in that when it is polymerized by irradiation with active energy rays, it easily transmits active energy rays. Incidentally, polypropylene is more preferable as the polyolefin.
  • the same kind of resin means that the main repeating units constituting the molecule (for example, when all the repeating units are 100 mol%, the main repeating units are 80 mol% or more) from the same monomer. It may have a repeating unit composed of a small amount of another monomer, and may have different molecular weights, different degrees of crystallinity, and the like.
  • a film through which the active energy ray is transmitted ie, a film transparent to the active energy ray
  • the transmittance of this active energy ray is preferably 5% or more, particularly preferably 30% or more.
  • it may be colorless and transparent, which is preferably colorless and transparent.However, it is transparent in the wavelength region where the polymerization initiator function of the polymerization initiator is exhibited. It is preferable that the property is high.
  • an electron beam it may be opaque visually, but it is preferable that the transparent force is at least high because at least the appearance can be confirmed through a film at the time of polymerization or the like.
  • the thickness of each of the first resin film and the second resin film is not particularly limited. Also, the thickness of each of the first resin film and the second resin film may be the same or different. The thickness of each of the first and second resin films is preferably 3100 x m, particularly 5 to 80 ⁇ , and more preferably 760 ⁇ m. If the thickness of each film is less than 3 ⁇ m, wrinkles are likely to occur and the precursor impregnated / adhered sheet may not be sufficiently supported during polymerization, which is not preferable. On the other hand, when the thickness exceeds 100 / m, when active energy rays are used for polymerization, the amount of active energy rays absorbed by the film increases, which is not preferable.
  • the first resin film and the second resin film have different thicknesses, and it is preferable that one is thin and the other is thick.
  • the active energy dose absorbed by the resin film can be reduced, and sufficient polymerization can be achieved with a small amount of active energy dose.
  • the precursor impregnated and adhered sheet can be supported by the thick resin film.
  • the thickness of the thin resin film is preferably 1 / 10-1Z2, especially 1 / 8-1 / 3, and more preferably 1 / 6-1 / 4 of the thickness of the thick resin film.
  • the thickness of the thin wood S-finolem is preferably 3 30 xm, especially 5-20 ⁇ , and more preferably 7 15 ⁇ m. If the thickness of the thin resin film is 330 ⁇ m, the polymer precursor can be efficiently polymerized. On the other hand, the thickness of the thick resin film is 35-80 zm, especially 40-65 xm, and more preferably 45-55 ⁇ m. If the thickness of the thick layer is 35,80 xm, the precursor impregnated / adhered sheet can be reliably supported. Note that the thickness variation of each of the first resin film and the second resin film is preferably ⁇ 10% or less, more preferably ⁇ 2% or less.
  • the first and second resin films may be directly contacted with the precursor-impregnated / adhered sheet as long as the polymer-filled / adhered sheet can be easily peeled off after the polymerization of the polymer precursor.
  • Body impregnation-Release agent may be applied to the surface that comes into contact with the adhered sheet and treated.
  • the release agent various types such as a silicone release agent, a fluorine release agent, a higher aliphatic release agent and the like can be used.
  • Precursor impregnation The method of polymerizing the polymer precursor impregnated and adhered to the adhered sheet is not particularly limited, and as described above, irradiation with active energy rays such as ultraviolet rays, electron beams, and visible rays. It can be carried out by polymerization, thermal polymerization by heating, or the like. Among these methods, polymerization by irradiation with active energy rays is preferable, and according to this method, a functional film can be easily and efficiently continuously produced. Further, as the active energy ray, an ultraviolet ray and an electron beam are more preferable. When ultraviolet rays are used, the apparatus is simpler than an electron beam, and is advantageous in terms of irradiation cost.
  • active energy rays such as ultraviolet rays, electron beams, and visible rays. It can be carried out by polymerization, thermal polymerization by heating, or the like. Among these methods, polymerization by irradiation with active energy rays is preferable, and according
  • the electron beam has excellent transparency to the porous resin sheet, and particularly when the porous resin sheet is made of a hydrocarbon-based polymer, a crosslinked structure can be introduced into the polymer depending on the irradiation conditions. Further, the polymerization by electron beam irradiation is preferable in that a radical photopolymerization initiator or the like is not required.
  • a radical photopolymerization initiator that generates radicals by ultraviolet rays is previously attached to the surface of the pores of the porous resin sheet.
  • the method for attaching the radical-type photopolymerization initiator is not particularly limited. Force The solution or dispersion containing the initiator is impregnated into the pores of the porous resin sheet, and then is attached by removing the solvent. Is preferred. In this case, the initiator can be uniformly attached to the pores of the porous resin sheet.
  • the radical-type photopolymerization initiator is not particularly limited, but may be a benzophenone-type, thioxanthone-type, thioacridone-type, or the like by extracting hydrogen from a carbon-hydrogen bond. Is preferred.
  • Benzophenone-based initiators include methyl o-benzoylbenzoate, 4-phenylphenylbenzophenone, 4_benzoyl-4'-methyldiphenyl sulfide, 3, 3 ', 4,4'-tetra (t_butylperoxycarboninole) ) Benzophenone, 2,4,6_trimethylbenzophenone, 4-benzoyl_N, N-dimethyl_N— [2- (1_oxy_2-provenyloxy) ethyl] benzenemethanamide Benzylbenzyl) trimethylammonium chloride, 4,4'-dimethylaminobenzophenone, 4,4'-ethylaminobenzophenone, and the like.
  • Examples of the thioxanthone-based initiator include thioxanthone, 2-chlorothioxanthone, 2,4-getylthioxanthone, 2-ethylthioxanthone, and the like. Further, examples of the thioacridone-based initiator include thioacridone.
  • radical-based photopolymerization initiator a benzoin-based, acetophenone-based, benzyl-based initiator, or the like can also be used.
  • benzoin-based initiator examples include benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin ethyl ether, benzoin isobutyl ether and the like.
  • acetophenone initiator examples include acetophenone, propiophenone, jetoxyacetophenone, 2,2-dimethoxy-11,2-diphenylethane-one, one-hydroxycyclohexylphenyl ketone, and 2-methyl-1_ ( 4- (Methylthio) pheninole)-2-Monfolinopropane-1,2-benzyl-12-dimethylamino-1- (4-morpholinophene) butanone_1,2-Hydroxy-12-methinole-1 —Feninolepropane-1-one, 1— (4_ (2-hydroxyethoxy) -1-pheninole) _2-hydroxydi-2-methinole 1_propane-1-one, and the like.
  • radical photopolymerization initiator Only one radical photopolymerization initiator may be used, or two or more radical photopolymerization initiators may be used.
  • the radical photopolymerization initiator is preferably used as a solution or dispersion as described above.
  • the concentration of the initiator in this solution or dispersion is preferably from 0.01 to 10% by mass, particularly preferably from 0.1 to 5% by mass. If the concentration is less than 0.01% by mass, polymerization may not be sufficiently performed. On the other hand, if it exceeds 10% by mass, the crystals of the initiator may precipitate and partially block the pores of the porous resin sheet. If a part of the pores is closed as described above, the polymer precursor or the like may not be sufficiently filled. Also, the entire porous resin sheet In some cases, it may not be filled evenly, and it is not preferable even if it is misaligned.
  • the acceleration voltage of the irradiated electron beam is preferably 150 to 500 KeV, particularly preferably 150 to 200 KeV, depending on the type of the polymer precursor. If the accelerating voltage is too low, electron beams are hardly generated. If the accelerating voltage is too high, the porous resin sheet may be deteriorated and its strength may be reduced.
  • the irradiation dose is preferably from 10 to 10,000 mj / cm 2 , more preferably from 100 to 5000 mj / cm 2 , and further preferably from 200 to 2000 mjZcm 2 , depending on the type of the polymer precursor.
  • the irradiation amount is less than 10 mj / cm 2 , the polymerizing force cannot be sufficiently increased. If the irradiation amount exceeds 10,000 mj / cm 2 , the strength of the porous resin sheet may deteriorate and the strength may decrease, which is not preferable.
  • post-hardening can be performed by irradiation with ultraviolet light or heating, if necessary.
  • a polymerization initiator for that purpose may be previously blended with the polymer precursor.
  • the polymerization initiator include azo compounds such as 2,2, -azobis (2-amidinopropane) dihydrochloride, ammonium persulfate, potassium persulfate, sodium persulfate, hydrogen peroxide, and benzoyl peroxide.
  • a peroxide such as tert-hydroperoxide, di-t_butyl peroxide, or the above-mentioned peroxide
  • a reducing agent such as sulfite, bisulfite, thiosulfate, formamidin sulfinic acid, or ascorbic acid.
  • examples include initiators, azo-based radical polymerization initiators such as 2,2, -azobis_ (2-amidinopropane) dihydrochloride, and azobissianovaleric acid.
  • One type of these polymerization initiators may be used, or two or more types may be used.
  • a method of post-curing it is preferable to cure by irradiation with ultraviolet rays, which can provide a desired functional film with good productivity by a simple process in which the polymerization reaction can be easily controlled.
  • the radical photopolymerization initiator those described above and the like can be used.
  • the amount of the radical photopolymerization initiator in the case where the polymer precursor is 100 mass%, 0.1 001 1 wt%, especially 0.5 001-0. 5 mass 0/0, further 0.01 0.5 it is preferable mass 0/0.
  • the first resin film and the second resin film may be kept in contact with the precursor-impregnated and adhered sheet.
  • the polymer precursor is formed in the pores of the porous resin sheet.
  • At least one of the first resin film and the second resin film may be peeled off as long as the polymerization proceeds to such an extent that the resin is sufficiently held in the inside. Then, by irradiating active energy rays such as ultraviolet rays from the side from which the resin film has been peeled, the irradiation efficiency is improved and post-curing can be performed efficiently.
  • the excess polymer precursor adhering to the surface of the porous resin sheet comes into contact with air to suppress the polymerization, and the polymer is filled in the subsequent polymer removal step.
  • the polymer adhering to the surface of the adhering sheet can be more easily removed.
  • the polymer adhering to the surface of the “polymer-filled adhering sheet” can be removed by a method such as wiping with a plastic blade made of polypropylene or the like.
  • the polymer-filled adhering sheet can be removed by contacting an adhering polymer removing tool.
  • the tool for removing the adhered polymer may be any as long as the functional film is not damaged and does not cause damage such as deformation. Examples of the attached polymer removing tool include a brush roll and a rubber blade.
  • the polymer adhering to the surface can also be removed by passing the polymer-filled adhering sheet through a narrow gap slightly wider than its thickness.
  • the impregnation, adhesion step, polymerization step, film peeling step and polymer removal step are performed continuously.
  • a long porous resin sheet is continuously conveyed and impregnated and adhered with a polymer precursor or the like to form a precursor impregnated / adhered sheet.
  • the first resin film and the second resin film are continuously supplied and contacted on one side and the other side, and the precursor impregnated / adhered sheet is sandwiched between the first and second resin films in this manner.
  • the polymer precursor is polymerized to form a polymer-filled adhesive sheet, and then the first and second resin films are peeled from the polymer-filled adhesive sheet, and then adhered to the surface of the polymer-filled adhesive sheet.
  • the removed polymer is removed.
  • a series of operations are performed by a continuous process.
  • the obtained long functional film can be stored as a product by a method such as continuous winding on a core.
  • the process is continuously performed including the other process.
  • This continuous manufacturing method can be performed, for example, by the steps shown in FIG. That is, the continuous porous resin sheet 1 that is continuously conveyed is brought into contact with a solution or dispersion 3 containing a polymer precursor or the like contained in a container (impregnation and adhesion step), and then the polymer precursor is contacted.
  • Precursor-impregnated body and soaked precursor-adhered and adhered sheet 11 is brought into contact with first resin film 21 and second resin film 22 continuously supplied from resin film supply sources 211 and 221 to impregnate precursor. 'Conveyed with the adhered sheet sandwiched between two resin films, irradiated with an electron beam, ultraviolet light, etc. from an active energy ray irradiation source E to polymerize the polymer precursor (polymerization step).
  • the first and second resin films are peeled off from the polymer-filled / adhered sheet in which the polymer is filled and adhered to the porous resin sheet (film peeling step), and then applied to the surface of the polymer-filled / adhered sheet 12.
  • the removed polymer is removed by removing it with a plastic blade 4 (polymer removal step), and then the removed polymer is washed away with water sprayed from Noznore N, and then dried by a drying device H as necessary. Then, the obtained functional film 5 can be continuously wound on a core to efficiently manufacture the film. Furthermore, in order to protect the product, the functional film to be wound can be wound while a protective film 6 made of polyester, polyolefin, fluororesin, or the like is laminated on at least one surface (both surfaces in FIG. 1).
  • steps other than the impregnation, adhesion step, polymerization step, film peeling step and polymer removal step include a drying step after the polymer removal step, an inspection step after this drying step, and a humidity control step. Can be These other steps are also performed as a series of continuous steps along with the impregnation, adhesion, polymerization, film peeling and polymer removal steps.
  • the functional membrane produced by the method of the present invention is an electrolyte membrane
  • this electrolyte membrane is useful as an electrolyte membrane in a polymer electrolyte fuel cell, particularly a direct methanol fuel cell.
  • a catalyst such as platinum
  • the electrolyte membrane electrode assembly integrated by a hot press or the like. Once formed, the assembly can be used in a fuel cell unit.
  • a body impregnated / adhered sheet 11 was prepared and then, as shown in FIG. 2, a polyethylene terephthalate film having a thickness of 50 zm (25 ° measured according to ASTM D 1434-72) Oxygen permeability in C is 385ml / m 2 '24 hours * MPa), and the film is transported with the precursor-impregnated / adhered sheet sandwiched by these films, and is the source E of active energy rays.
  • the film UV after transparently is irradiated with ultraviolet rays so that the irradiation dose of 2000 mJ / cm 2 in total to polymerize the poly-mer precursor, then, peeling the polyethylene terephthalate film from both sides Then, the polymer adhering to the surface of the polymer-filled adhering sheet was removed with a polypropylene blade.
  • the obtained electrolyte membrane was translucent, and its surface was not damaged such as scratches, deformation, and tears.
  • the thickness of one side of the polyethylene terephthalate film was reduced to 10 ⁇ m, and ultraviolet light was irradiated only from the thin side. Then, an electrolyte membrane was produced in the same manner as in Example 1 except that the irradiation amount of the ultraviolet light after passing through the film was set to 2000 mj / cm 2 .
  • the obtained electrolyte membrane was translucent, and its surface had no damage such as scratches, deformation, or tears. Further, in Example 2, the thickness of the film that transmits ultraviolet light was 1/5 of that of Example 1, and thus the amount of ultraviolet light before transmission through the film could be reduced by half.
  • An electrolyte membrane was manufactured in the same manner as in Example 1 except that the polyethylene terephthalate film was not brought into contact with the film and that the film was not in contact.
  • the obtained electrolyte membrane was a non-homogeneous membrane having defects where the polymer was not filled. Therefore, it is not possible to evaluate as an electrolyte membrane described later I got it.
  • Example 1 50 ml of the solution prepared in Example 1 was placed in a Petri dish, and a test piece of 5 cm in length and width cut out from a porous polyethylene resin sheet was immersed in the solution to impregnate the polymer precursor and the like. Force The test piece taken out was sandwiched between glass plates, and irradiated with ultraviolet light at a dose of 1000 mj / cm 2 from one side after passing through the glass using a high-pressure mercury lamp for experiments. After that, it was turned upside down and irradiated with the same amount of ultraviolet rays from the opposite side. Next, the glass plate was removed, and the polymer adhering to the surface was removed with a polypropylene blade to obtain an electrolyte membrane. This electrolyte membrane was translucent, and its surface was not damaged such as scratches, deformation, and tears.
  • the electrolyte membrane was immersed in water at 25 ° C to swell, and then the electrolyte membrane was sandwiched between two platinum foil electrodes to prepare a specimen for measuring proton conductivity. Using this specimen, the impedance was measured by an impedance measuring device (Hewlett-Packard Co., model “HP4192A”).
  • the pervaporation experiment at 50 ° C was carried out using methanol / water at a mass ratio of 1/9 as a feed solution, reducing the pressure on the permeation side until the permeation flow rate became steady. Details are as follows.
  • the electrolyte membrane was sandwiched between stainless steel cells, and the above-mentioned supply liquid was poured into the upper surface of the electrolyte membrane and stirred.
  • a heater and a resistance temperature detector were charged into the supply liquid, and the temperature was controlled at 50 ° C.
  • a vacuum pump was connected to the lower surface of the electrolyte membrane via a cold trap. In this way, the lower surface of the electrolyte membrane, that is, the permeation side was depressurized, and the mixture of methanol and water vapor that had permeated the electrolyte membrane was collected in the cold trap.
  • the collected vapor solidified in the cold trap
  • the total permeation flux is determined from the mass thereof and the permeated vapor composition is determined by gas chromatography analysis. , Respectively. This measurement was continued until the membrane permeability became constant with respect to time, and the measured value at the time when the membrane permeability became constant was evaluated as steady-state permeability.
  • a polyimide precursor NMP solution containing a total of 8.3% by mass of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and oxydianiline in a molar ratio of 0.999 is mirror-polished.
  • the precursor impregnated 'adhesion sheet 11 is prepared, and then a 50 ⁇ m-thick polyethylene terephthalate film is brought into contact with both surfaces of the precursor impregnation-adhesion sheet as shown in FIG.
  • the film is conveyed with the precursor-impregnated and adhered sheet sandwiched between these films, and heated at 60 ° C. instead of the ultraviolet irradiation in Example 1 to polymerize the polymer precursor, and then both sides are irradiated.
  • the polyethylene terephthalate film was peeled off, and then the polymer adhering to the surface of the polymer-filled sheet was removed with a polypropylene blade.
  • the obtained electrolyte membrane was translucent and had a darker color than the polyimide porous film.
  • the surface had good appearance without damage such as scratches, deformation and tearing.
  • the mass of this electrolyte membrane was increased by 23% by mass compared to the polyimide porous film.
  • FIG. 1 is a flowchart showing an example of a process for manufacturing a functional film.
  • FIG. 2 The first resin film and the second resin film are each continuously fed and supplied with a film supply power, and are irradiated with an active energy ray in a state where the first resin film and the second resin film are in contact with the precursor-impregnated / adhered sheet. It is explanatory drawing which shows the method of superposing
  • FIG. 3 The first resin film is continuously fed and supplied with the film supply power.
  • the precursor is impregnated.
  • the second resin film is brought into contact with the adhesive sheet to form a closed loop in the longitudinal direction.
  • FIG. 4 is an explanatory view showing a method of polymerizing a polymer precursor by irradiating active energy rays in a state where the film is rotated and continuously contacted with a precursor impregnated / adhered sheet while rotating the film.
  • FIG. 4 is an explanatory view showing a method of polymerizing a polymer precursor by irradiating an active energy ray in a state where an agglutination sheet and both films are continuously contacted.
  • porous resin sheet polyethylene porous resin sheet
  • 11 precursor-impregnated 'attached sheet'
  • 12 polymer-filled 'adhered sheet
  • 21 first resin film
  • 22 second resin film
  • 211, 221 film source
  • 3 solution or dispersion containing a polymer precursor, etc .
  • E active energy ray irradiation source
  • 4 plastic blade
  • N spraying water for washing Nozzle
  • H drying equipment
  • 5 functional membrane
  • 6 protective film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Fuel Cell (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Conductive Materials (AREA)

Abstract

L'invention concerne un procédé de production en continu d'un film fonctionnel consistant à transporter en continu une feuille de résine poreuse (une feuille de polyéthylène poreuse ou analogue) et à l'imprégner d'un précurseur polymère ayant un groupe fonctionnel (un acide 2-acrylamide-2-méthylpropanesuflonique ou analogue), afin de fixer le précurseur polymère sur la feuille en résine poreuse, à effectuer une polymérisation, au cours de laquelle des premier et second films de résine (tous 2 étant un film polyester ou analogue) sont acheminés en continu sur les surfaces de la feuille poreuse ayant été imprégnée avec le précurseur polymère précité et contenant le précurseur polymère, de manière que les films de résine entrent en contact avec les surfaces et que la feuille poreuse soit mise en sandwich entre les deux films de résine, puis à polymériser le précurseur polymère (par le rayonnement avec un rayon d'énergie active et analogue), à libérer le film et à retirer le polymère. Le procédé permet la production d'un film fonctionnel ayant une feuille de résine poreuse contenant un polymère fonctionnel dans ses pores de manière continue et très efficace.
PCT/JP2004/006389 2003-09-03 2004-05-12 Procede de production en continu d'un film fonctionnel WO2005023921A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CA002537795A CA2537795A1 (fr) 2003-09-03 2004-05-12 Procede de production en continu d'un film fonctionnel
US10/570,609 US7674349B2 (en) 2003-09-03 2004-05-12 Method for continuous production of a functional film

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003311841A JP4427291B2 (ja) 2003-09-03 2003-09-03 機能性膜の連続製造方法
JP2003-311841 2003-09-03

Publications (1)

Publication Number Publication Date
WO2005023921A1 true WO2005023921A1 (fr) 2005-03-17

Family

ID=34269714

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2004/006389 WO2005023921A1 (fr) 2003-09-03 2004-05-12 Procede de production en continu d'un film fonctionnel

Country Status (4)

Country Link
US (1) US7674349B2 (fr)
JP (1) JP4427291B2 (fr)
CA (1) CA2537795A1 (fr)
WO (1) WO2005023921A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007094279A1 (fr) 2006-02-15 2007-08-23 Toagosei Co., Ltd. Procede de production d'une membrane fonctionnelle
EP1890351A1 (fr) * 2005-05-18 2008-02-20 Toagosei Co., Ltd. Dispositif d' electrodes a membrane et pile a combustible a utilisation directe de combustible liquide
WO2008081802A1 (fr) * 2006-12-26 2008-07-10 Toyo Boseki Kabushiki Kaisha Procédé de fabrication d'une membrane électrolytique polymère
EP2149172A1 (fr) * 2007-05-15 2010-02-03 LG Chem, Ltd. Batterie rechargeable et son procédé de fabrication
CN110197919A (zh) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 一种全钒液流电池用离子传导型多孔隔膜及其制备法和用途

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006160837A (ja) * 2004-12-03 2006-06-22 Toagosei Co Ltd 電解質膜の製造方法
JP4525329B2 (ja) * 2004-12-13 2010-08-18 東亞合成株式会社 電解質膜の連続製造方法
JP2007273450A (ja) * 2006-03-08 2007-10-18 Toyota Motor Corp 電解質膜及びその製造方法
JP4997625B2 (ja) * 2006-03-24 2012-08-08 独立行政法人日本原子力研究開発機構 燃料電池用高分子電解質膜の製造方法、その電解質膜、およびその膜を使用した燃料電池用膜電極接合体
US20090098359A1 (en) 2007-10-11 2009-04-16 Waller Jr Clinton P Hydrophilic porous substrates
GB0812187D0 (en) * 2008-07-03 2008-08-13 Dow Corning Modified polyethylene
GB0812186D0 (en) * 2008-07-03 2008-08-13 Dow Corning Modified polyolefins
EP2401065B1 (fr) * 2009-02-27 2017-12-13 EMD Millipore Corporation Membrane à groupes sulfoniques pour l'élimination d'agrégats de protéines
US8211335B2 (en) * 2009-08-31 2012-07-03 General Electric Company Method for making polymer, coating electrode, and associated polymer and electrode
GB0915109D0 (en) * 2009-09-01 2009-10-07 Fujifilm Mfg Europe Bv Process for preparing composite membranes
GB0921949D0 (en) 2009-12-16 2010-02-03 Fujifilm Mfg Europe Bv Curable compositions and membranes
GB0921951D0 (en) 2009-12-16 2010-02-03 Fujifilm Mfg Europe Bv Curable compositions and membranes
JP2011170690A (ja) * 2010-02-19 2011-09-01 Sony Corp 情報処理装置、情報処理方法、およびプログラム。
JP2012046566A (ja) * 2010-08-24 2012-03-08 Toagosei Co Ltd 電子線硬化型組成物及び樹脂フィルム又はシート
WO2013014420A1 (fr) 2011-07-25 2013-01-31 Fujifilm Manufacturing Europe Bv Membranes composites
WO2013077347A1 (fr) * 2011-11-22 2013-05-30 住友電気工業株式会社 Diaphragme pour des batteries à flux redox
CN102582200B (zh) * 2011-11-27 2014-07-09 中国海诚工程科技股份有限公司 一种锂电池隔膜预干燥薄膜转移涂布的装置和方法
WO2014039171A2 (fr) 2012-09-07 2014-03-13 General Electric Company Procédés de fabrication de membranes échangeuses d'ion
EP2842620A1 (fr) 2013-08-26 2015-03-04 Agfa-Gevaert Procédé de préparation d'une membrane composite
KR101511990B1 (ko) * 2013-09-24 2015-04-14 한국에너지기술연구원 역전기투석 장치용 이온 교환막 및 이를 포함하는 역전기투석 장치
CN105980047B (zh) 2013-12-12 2019-01-04 Emd密理博公司 使用含丙烯酰胺的过滤器分离蛋白
JP2015153653A (ja) * 2014-02-17 2015-08-24 株式会社Ｓｃｒｅｅｎホールディングス 電解質膜改質装置および電解質膜改質方法、並びに、膜・触媒層接合体の製造システムおよび製造方法
ES2772426T3 (es) * 2014-09-11 2020-07-07 Fujifilm Corp Composición para formar membrana funcional polimérica, membrana funcional polimérica y proceso de producción para la misma, módulo de membrana de separación e intercambiador iónico
EP3278867B1 (fr) 2015-03-31 2021-09-08 Toray Industries, Inc. Membrane de séparation
JP2016207609A (ja) * 2015-04-28 2016-12-08 東洋紡株式会社 複合高分子電解質膜およびその製造方法ならびに膜電極接合体、燃料電池
JP2016207610A (ja) * 2015-04-28 2016-12-08 東洋紡株式会社 複合高分子電解質膜およびその製造方法ならびに膜電極接合体、燃料電池
CN106362599A (zh) * 2016-08-29 2017-02-01 无锡零界净化设备有限公司 一种无支撑层微孔平板滤膜的制备方法
CN107785613B (zh) * 2016-12-01 2020-05-19 万向一二三股份公司 锂电池隔膜在线干燥方法
KR102133787B1 (ko) 2018-05-02 2020-07-15 도레이첨단소재 주식회사 표면 이온 교환 고분자 전해질이 제거된 세공충진 이온 교환 고분자 전해질 복합막 및 이의 제조방법
KR102036766B1 (ko) * 2018-05-24 2019-10-25 도레이케미칼 주식회사 바나듐 이온 저투과를 목적으로 하는 세공충진형 양쪽성막 및 이의 제조방법
US11791479B2 (en) * 2018-08-10 2023-10-17 Ess Tech, Inc. Methods and system for manufacturing a redox flow battery system by roll-to-roll processing
CN109927220A (zh) * 2019-01-29 2019-06-25 浙江隆劲电池科技有限公司 一种连续制备及转移固态电解质膜的方法
US20220407179A1 (en) * 2019-11-08 2022-12-22 Lg Energy Solution, Ltd. Crosslinked Separator for Lithium Secondary Battery Including Crosslinked Polyolefin and Method for Manufacturing the Same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198640A (ja) * 1987-10-12 1989-04-17 Sumitomo Electric Ind Ltd 親水性四弗化エチレン樹脂多孔質膜の製造方法
JP2000053788A (ja) * 1998-08-12 2000-02-22 Japan Atom Energy Res Inst 放射線グラフト重合方法
JP2000235849A (ja) * 1998-12-14 2000-08-29 Sumitomo Electric Ind Ltd 電池用隔膜
JP2000273229A (ja) * 1999-03-25 2000-10-03 Nitto Denko Corp 親水化した疎水性基材の製造方法
JP2001135328A (ja) * 1999-11-01 2001-05-18 Tokuyama Corp 固体高分子電解質型燃料電池用隔膜

Family Cites Families (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1192394B (de) * 1968-02-07 1965-05-06 Fmc Corp Vorrichtung zur Herstellung von armierten Kunststoffrohren
US3612282A (en) * 1969-08-14 1971-10-12 Sing Wang Cheng Supporting structures and containing vessels for reverse osmosis and filtration
US3648845A (en) * 1969-09-02 1972-03-14 Us Interior Thin film separation membranes and processes for making same
US3951815A (en) * 1974-09-05 1976-04-20 Universal Oil Products Company Composite semipermeable membranes made from polyethylenimine
US4151053A (en) * 1975-07-09 1979-04-24 Asahi Kasei Kogyo Kabushiki Kaisha Cation exchange membrane preparation and use thereof
DE2925969A1 (de) * 1979-06-27 1981-01-29 Fraunhofer Ges Forschung Poroese membranen und adsorbentien, verfahren zu ihrer herstellung und ihre verwendung zur stofftrennung
DE3066996D1 (en) * 1979-09-19 1984-04-19 Aligena Ag Porous semipermeable cellulose acetate membranes modified by ionic groups, process for their production and their use
US4707265A (en) * 1981-12-18 1987-11-17 Cuno Incorporated Reinforced microporous membrane
US4529646A (en) * 1984-07-30 1985-07-16 E. I. Du Pont De Nemours And Company Production of composite membranes
US4610762A (en) * 1985-05-31 1986-09-09 The Dow Chemical Company Method for forming polymer films having bubble release surfaces
CA1314667C (fr) * 1986-05-30 1993-03-23 Hajime Itoh Procede de production de membranes poreuses
USRE34115E (en) * 1986-07-25 1992-10-27 Albany International Corp. Method for modifying asymmetric membranes by endo-treating
US4784880A (en) * 1986-07-25 1988-11-15 Albany International Corp. Method for modifying asymmetric membranes by endo-treating
US5030355A (en) * 1987-10-14 1991-07-09 Exxon Research & Engineering Company Thin film composite membrane prepared by suspension deposition
JPH0761428B2 (ja) * 1989-03-09 1995-07-05 松下電器産業株式会社 選択透過性膜およびその製造方法
US4996098A (en) * 1989-02-28 1991-02-26 E. I. Du Pont De Nemours And Company Coated cation exchange fabric and process
US5202025A (en) * 1989-04-12 1993-04-13 Terumo Kabushiki Kaisha Porous membrane and method for preparing the same
EP0606309B1 (fr) * 1991-10-04 1995-08-30 Alcan International Limited Structures laminees detachables et procede de fabrication
EP0746582B1 (fr) * 1993-04-27 2000-03-15 Cytotherapeutics, Inc. Membrane formee par un polymere a base d'acrylonitrile
WO1996009110A1 (fr) * 1994-09-20 1996-03-28 Graham John Bratton Membrane perfectionnee
US5837365A (en) * 1996-04-08 1998-11-17 The Penn State Research Foundation Hydrophilic polypropylene membranes
CN1130415C (zh) * 1996-12-10 2003-12-10 大赛璐化学工业株式会社 多孔膜、其制备方法及由多孔膜制成的叠层膜和记录片材
US6264044B1 (en) * 1997-04-11 2001-07-24 Cuno, Inc. Reinforced, three zone microporous membrane
US6354443B1 (en) * 1997-05-01 2002-03-12 Millipore Corporation Surface modified porous membrane and process
US6723758B2 (en) * 1997-11-12 2004-04-20 Ballard Power Systems Inc. Graft polymeric membranes and ion-exchange membranes formed therefrom
US6015495A (en) * 1998-02-18 2000-01-18 Saehan Industries Incorporation Composite polyamide reverse osmosis membrane and method of producing the same
JPH11335473A (ja) 1998-05-26 1999-12-07 Tokuyama Corp イオン交換膜およびその用途
US6287717B1 (en) * 1998-11-13 2001-09-11 Gore Enterprise Holdings, Inc. Fuel cell membrane electrode assemblies with improved power outputs
US6468657B1 (en) * 1998-12-04 2002-10-22 The Regents Of The University Of California Controllable ion-exchange membranes
WO2000043113A1 (fr) * 1999-01-22 2000-07-27 Membrana Gmbh Procede de fabrication d'une membrane polyolefinique integralement asymetrique
AU2831000A (en) * 1999-03-08 2000-09-28 Center For Advanced Science And Technology Incubation, Ltd. Electrolytic membrane for fuel cell and its manufacturing method, and fuel cell and its manufacturing method
US6337018B1 (en) * 2000-04-17 2002-01-08 The Dow Chemical Company Composite membrane and method for making the same
JP4228062B2 (ja) 2002-10-24 2009-02-25 東洋紡績株式会社 多孔膜、複合イオン交換膜およびその製造方法
US7338692B2 (en) * 2003-09-12 2008-03-04 3M Innovative Properties Company Microporous PVDF films
US7259208B2 (en) * 2003-11-13 2007-08-21 3M Innovative Properties Company Reinforced polymer electrolyte membrane

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0198640A (ja) * 1987-10-12 1989-04-17 Sumitomo Electric Ind Ltd 親水性四弗化エチレン樹脂多孔質膜の製造方法
JP2000053788A (ja) * 1998-08-12 2000-02-22 Japan Atom Energy Res Inst 放射線グラフト重合方法
JP2000235849A (ja) * 1998-12-14 2000-08-29 Sumitomo Electric Ind Ltd 電池用隔膜
JP2000273229A (ja) * 1999-03-25 2000-10-03 Nitto Denko Corp 親水化した疎水性基材の製造方法
JP2001135328A (ja) * 1999-11-01 2001-05-18 Tokuyama Corp 固体高分子電解質型燃料電池用隔膜

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1890351A1 (fr) * 2005-05-18 2008-02-20 Toagosei Co., Ltd. Dispositif d' electrodes a membrane et pile a combustible a utilisation directe de combustible liquide
EP1890351A4 (fr) * 2005-05-18 2010-11-03 Toagosei Co Ltd Dispositif d' electrodes a membrane et pile a combustible a utilisation directe de combustible liquide
WO2007094279A1 (fr) 2006-02-15 2007-08-23 Toagosei Co., Ltd. Procede de production d'une membrane fonctionnelle
JPWO2007094279A1 (ja) * 2006-02-15 2009-07-09 東亞合成株式会社 機能性膜の製造方法
JP4640503B2 (ja) * 2006-02-15 2011-03-02 東亞合成株式会社 機能性膜の製造方法
WO2008081802A1 (fr) * 2006-12-26 2008-07-10 Toyo Boseki Kabushiki Kaisha Procédé de fabrication d'une membrane électrolytique polymère
US8304133B2 (en) 2006-12-26 2012-11-06 Toyo Boseki Kabushiki Kaisha Method for producing a polymer electrolyte membrane
EP2149172A1 (fr) * 2007-05-15 2010-02-03 LG Chem, Ltd. Batterie rechargeable et son procédé de fabrication
EP2149172A4 (fr) * 2007-05-15 2010-11-03 Lg Chemical Ltd Batterie rechargeable et son procédé de fabrication
US8603682B2 (en) 2007-05-15 2013-12-10 Lg Chem, Ltd. Secondary battery and manufacturing method of the same
CN110197919A (zh) * 2018-02-27 2019-09-03 湖南省银峰新能源有限公司 一种全钒液流电池用离子传导型多孔隔膜及其制备法和用途

Also Published As

Publication number Publication date
CA2537795A1 (fr) 2005-03-17
JP4427291B2 (ja) 2010-03-03
US20080216942A1 (en) 2008-09-11
US7674349B2 (en) 2010-03-09
JP2005076012A (ja) 2005-03-24

Similar Documents

Publication Publication Date Title
WO2005023921A1 (fr) Procede de production en continu d'un film fonctionnel
US12036747B2 (en) Laminate, method for manufacturing laminate, and shape control device
EP1339072A1 (fr) (membranes) composites de polyelectrolytes solides portant des groupes d'acide phosphorique et leurs procedes de production
KR20030090779A (ko) 중합체 전해질 막
AU2015370441B2 (en) Asymmetric composite membranes and modified substrates used in their preparation
CN101497001A (zh) 一种单片型双极性离子交换膜及其制备方法
JP5120543B2 (ja) 陽イオン交換膜およびその製造方法
CN102698608A (zh) 一种具有永久亲水性和永久抗菌性的超滤膜制备方法
WO2006046620A1 (fr) Matériau électrolytique, membrane électrolytique et ensemble d’électrode à membrane pour pile à combustible polymère solide
KR20060134197A (ko) 전해질막 및 막전극 접합체의 제조 방법, 및 연료 전지
JP4192730B2 (ja) 機能性膜の連続製造方法
JP2004335119A (ja) 電解質膜および当該電解質膜を用いた燃料電池
JP4525329B2 (ja) 電解質膜の連続製造方法
JP2001313057A (ja) 固体高分子型燃料電池用イオン交換性フィルタの製造方法
JP3423765B2 (ja) イオン交換膜の積層方法
WO2005076396A1 (fr) Film électrolytique et pile à combustible utilisant le film électrolytique
JP2006160837A (ja) 電解質膜の製造方法
JP2006073495A (ja) ポリアクリロニトリル多孔質膜にリン酸基含有不飽和単量体（組成物）を含浸させ、（共）重合してなる固体高分子電解質複合膜及びその用途
JP2008189864A (ja) 機能性膜の製造方法
US11291215B2 (en) Durable asymmetric composite membranes and modified substrates used in their preparation
JP2009093919A (ja) 芳香族ポリエーテル系電解質膜の製造方法
WO2008059734A1 (fr) Membrane électrolyte polymère et procédé de production de membrane électrolyte polymère
WO2008029761A1 (fr) Procédé de fabrication d'une membrane fonctionnelle
JP2006172764A (ja) 電解質膜の製造方法
KR102211640B1 (ko) Uv 반응성 관능기가 함유된 고분자를 이용한 uv 가교 기체 분리막의 제조방법 및 이에 따라 제조되는 기체 분리막

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NA NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2537795

Country of ref document: CA

122 Ep: pct application non-entry in european phase
WWE Wipo information: entry into national phase

Ref document number: 10570609

Country of ref document: US